This invention relates in one aspect to low density, closed-cell foams which are made from blends of non-ionic ethylenic polymers and substantially non-neutralized carboxylated copolymers of ethylene with a monoethylenically unsaturated carboxylic acid. In another aspect, this invention pertains to an improvement whereby dimensionally stable low density, closed-cell ethylenic polymer foams can be obtained using blowing agents which otherwise do not produce foams having satisfactory dimensional stability. In yet another aspect, this invention relates to dimensionally stable soft ethylenic polymer foams made from blends comprising non-ionic copolymers of ethylene having relatively low modulus (i.e., materials lacking stiffness and which are limp, flexible and easily stretched).
The term "stiffness" as used herein means the property of plastics as determined by the test procedure described in ASTM D-747, expressed in pounds per square inch (psi).
It is well known to make closed-cell ethylenic polymer resin foams by the process of extrusion foaming wherein a normally solid thermoplastic ethylenic polymer resin such as polyethylene is heat-plastified and mixed under pressure with a volatile material such as 1,2-dichlorotetrafluoroethane to form a flowable gel which is then passed through a shaping orifice or die opening into a zone of lower pressure. Upon the release of pressure, the volatile constituent of the gel vaporizes, forming a gas phase cellular structure which cools to a corresponding cellular foamed solid resin. Desirably, the resulting cells are substantially uniform in size, uniformly distributed through the foam body, and closed, i.e., separated from each other by membrane walls of resin. Although a number of general principles are thought to be understood, much of the extrusion foaming technology remains empirical, based on experience, and is directed to very specific materials and details to produce saleable products of narrowly defined specification.
One of the common requirements of acceptable foam resin products is dimensional stability. That is, in such products, it is generally desired that the linear dimensions and thus the volume of a piece of foam resin not change appreciably, either to shrink or to expand, under ordinary conditions, from the time its manufacture is complete until the time its ultimate useful life is ended. It is also desired that if any appreciable shrinking of the foam is to occur, which is often the case with a freshly extruded foam, the foam be able to recover within a reasonable period of time to a substantially constant volume close to that of the foam measured shortly after its extrusion. The difficulties of attaining dimensional stability are particularly acute in foams of relatively low density (high expansion ratio) when the resin membrane cell walls are relatively thin. It has been explained that the vapors of volatile material originally present in the cell gradually permeate the cell wall and escape from the foam over a period of time, thereby tending to reduce the inner cell pressure and tending to cause the foam to shrink during that time. However, when the foam is exposed to ambient atmosphere, air and its constituent gases also tend to permeate into the foam through the cell wall over a period of time thereby tending to increase the inner cell pressure. Accordingly, the actual change in cell gas pressure and size is the result of complex and often opposite forces, and the resultant effect on resin foam dimensions is difficult to predict.
Although many volatile hydrocarbons, chlorohydrocarbons, fluorocarbons, and chlorofluorocarbons, as well as volatile ethers, ketones and other materials have been suggested for making extrusion foamed resin products, most are unsatisfactory in one or more respects when used individually. It has been suggested to use mixtures of two or more of such agents, or mixtures thereof with materials not useable alone, in attempt to achieve a favorable balance of the various properties of interest in a given instance. In U.S. Pat. No. 3,766,099, for example, polyethylene is foamed by extrusion of a flowable gel containing a mixture of (A) dichlorodifluoromethane and (B) at least one of monochloropentafluoroethane and octafluorocyclobutane in certain proportions of (B) to (A) and optionally (C) one or more of certain aliphatic hydrocarbons or chlorofluorohydrocarbons. Under certain conditions, the gel is said to produce relatively stable foam products from polyethylene, whereas dichlorodifluoromethane alone produced foams showing considerable shrinkage on storage in air after production. However, the idea of using mixtures of volatile materials as blowing agents introduces even more complexity into the consideration of foaming behavior and makes prediction of results even more difficult.
These difficulties are even greater where, in place of polyethylene, there is used an ethylenic polymer resin having less stiffness, i.e., lower flexural modulus, than that of polyethylene such as, for example, copolymers of ethylene and vinyl acetate (EVA) having stiffness (ASTM D-747) less than 20,000 psi. When such soft copolymers are used, the resulting foam is very sensitive to imbalances of rates of diffusion of the residual blowing agent out of the resin and out of the cells and air into such cells so that the tendency for dimensional instability, e.g., shrinking or expanding, is even greater than for stiffer resins and foams. For example, although U.S. Pat. No. 3,766,099 alleges that its process and mixed blowing agents can be used for foaming EVA resins in place of polyethylene, the fact is that, when the system preferred for use with polyethylene is used with a soft, low-stiffness EVA resin to make a low density foam, the resulting foam is dimensionally unstable and shrinks excessively on exposure to air, and there is no direction or instruction in the patent to correct the situation and to provide a satisfactory product.
In U.S. Pat. No. 4,101,467 low density closed-cell, soft foam products having dimensional stability are made from ethylenic resins having low stiffness, especially from copolymers consisting essentially of ethylene and monoethylenically unsaturated non-ionic comonomers by the process of extrusion foaming. The process is particularly characterized in that the volatile blowing agent is composed of at least two essential constituents having certain physical characteristics. Exemplary mixtures contain (I) 1,2-dichloro-1,1,2,2-tetrafluoroethane and (II) from 25 to 50 percent chloropentafluoroethane, octafluoropropane or octafluorocyclobutane based on the mixtures of (I) and (II). In U.S. Pat. No. 4,129,530, similar soft foam products are made using an exemplary mixture containing (I) dichlorodifluoromethane and (II) from 35 to 50 percent chloropentafluoroethane, octafluoropropane or octafluorocyclobutane based on the mixtures of (I) and (II). However, using mixtures of volatile materials as blowing agents introduces more complexity into the extrusion foaming process with related process difficulties. Furthermore, there is need and desire for improved and/or alternate processes which are less difficult to carry out. It is also desirable to have such soft foam products having improved physical properties, especially for use in constructing items of wearing apparel, particularly for cushioning in sports equipment and athletic padding and for flotation in vests for water skiers, boating safety jackets and the like.
U.S. Pat. No. 4,102,829 discloses a thermoplastic foam characterized by low density, high thermal resistance, good adhesion properties and uniform cell size which comprises a mixture containing from 35 percent to 95 percent ionomer characterized by the presence of a monomer unit based on an unsaturated carboxylic acid and 5 percent to 65 percent polyolefin polymer or copolymer, based on the total weight of resin; the ethylene monomer unit and unsaturated carboxylic acid ester monomer unit values of the ionomer being from 50 to 97 mol percent and up to 30 mol percent, respectively, the neutrality value of the ionomer being up to 50 percent, the saponification value of the ionomer being at least 50 percent, and the melt index of the ionomer being from 0.1 to 50 g/10 min.; the melt index of the polyolefin being from 0.1 to 30 g/10 min. However, such patent does not contemplate low density, closed-cell, soft foam products being dimensionally stable from a polymer blend comprising a substantially non-neutralized copolymer of ethylene and carboxylic acid and a non-ionic ethylenic polymer.
U.S. Pat. No. 4,110,269 discloses a method of producing a low density polyethylene foam comprising charging an extruder with a polyethylene resin, from about 5 percent to 30 percent by weight of an ionomer resin selected from the group consisting of ionically crosslinked copolymers of ethylene/methacrylic acid and ethylene/vinyl acetate, and a nucleating agent, heating said charge so as to melt said resins, injecting an expanding agent mixture consisting of dichlorodifluoromethane and dichlorotetrafluoroethane into said melt charge in an amount of 8 percent or less by weight, said mixture comprises approximately a 2:1 ratio of dichlorotetrafluoroethane to dichlorodifluoromethane, and extruding said melt charge to form said foam. This reference also does not contemplate the use of substantially non-neutralized carboxylated ethylenic polymers as is required in the practice of the present invention.
An object of this invention is to provide dimensionally stable, low density foams of ethylenic polymer resins. Another object is to provide a method and a means for improving the dimensional stability of ethylenic polymer foams which otherwise have relatively poor dimensional stability. A particular object is to provide such improved method and a means for making soft, flexible, substantially closed-cell, low density polymer resin blend foams from ethylenic polymer resins which have low stiffness. Other objects and advantages of the invention are brought out in the description that follows.